Acrylic and methacrylic monomers, polymers and copolymers

ABSTRACT

A new class of polymers comprising a main carbon chain and having polyfluoropolyether side groups. The polymers possess excellent soil and water resistant properties and are useful for rendering fabrics soil and moisture resistant. The polymers are prepared from a new class of polymerizable polyfluorinated polyether acrylates, methacrylates, acrylamides and methacrylamides. A new class of alcohols, useful for preparing the acrylate and methacrylate monomers is disclosed and methods for preparing the alcohols, monomers and polymers are disclosed.

Caporiccio et al.

Feb. 4, 1975 ACRYLIC AND METHACRYLIC MONOMERS, POLYMERS AND COPOLYMERSInventors: Gerardo Caporiecio, Milan; Ezio Strepparola, Treviglio, bothof Italy Assignee: Monteratini Edison S.p.A, Milan,

Italy Filed: June 25, 1973 Appl. No.: 373,268-

Related U.S. Application Data Division of Ser. No. 108,573, Jan. 2],197], Pat. No. 3,766,251,

Foreign Application Priority Data Jan. 24, 1970 ltaly l9750/70 U.S. Cl.260/80.3 N, ll7/l40, 117/161, 260/86.1 E, 260/89.5 H, 260/89.5 S,

260/89.7 R, 260/486 H, 260/561 N Int. Cl C08f 3/90, C08f 15/02 Field ofSearch 260/89.7 R, 80.3 N, 80.73

[56] References Cited UNITED STATES PATENTS 2,957,9l4 l0/l960 Halpern etal. H 260/89.7 R 3,544,537 12/1970 Brace 260/8073 3,553,179 l/l97lBartlett 260/80.3 N

Primary Examiner-Harry Wong, Jr. Attorney, Agent, or Firm-Hubbell, Cohenand Stiefel [57] ABSTRACT A new class of polymers comprising a maincarbon chain and having polyfluoropolyether side groups. The polymerspossess excellent soil and water resistant properties and are useful forrendering fabrics soil and moisture resistant. The polymers are preparedfrom a new class of polymerizable polyfluorinated polyether acrylates,methacrylates, acrylamides and methacrylamides. A new class of alcohols,useful for preparing the acrylate and methacrylate monomers is disclosedand methods for preparing the alcohols, monomers and polymers aredisclosed.

9 Claims, No Drawings ACRYLIC AND METHACRYLTC MONOMERS, POLYMERS ANDCOPOLYMERS CROSS-REFERENCE TO RELATED APPLICATIONS This is a division ofco-pending application Ser. No. 108,573, filed on Jan. 21, 197], now USPat. No. 3,766.25l.

BACKGROUND OF THE INVENTION 1. Field of the lnvention The presentinvention relates to a new class of monomeric acrylic and methacrylicderivatives of compounds having a linear polyfluoropolyether structure,and to homopolymers and co'polymers thereof. These monomeric compoundscan be polymerized to form elastomeric polymers possessing manydesirable properties by virtue of the polyfluoroether structure which ispresent as a side chain group on the main polymer chain.

2. Description of the Prior Art Polymers derived from oleflnic monomersand having fluorine-containing side groups attached to the main carbonchain are known. Such polymers frequently have certain desirableproperties. For example, they are normally elastomers or rubberypolymers which can be vulcanized to produce rubbers having lowtemperature flexibility, excellent resistance to oxidation by air,resistance to oils and lubricants, etc..

A polymer ofthis type is illustrated in British Pat. No. 703,435 whereinthe polymerization of an ester of acrylic acid and al,l-dihydroperfluoroalkyl alcohol is disclosed. US Pat. No. 2,839,5l3,discloses fluorinated acrylate esters which can be used to prepare theforegoing described polymers, which esters contain a terminallyhydrogenated carbon atom and an oxa" atom, i.e., an oxygen atom in placeof a carbon atom in the carbon chain of the fluoropolymer. Such estersare illustrated by the compound l,l,6-trihydro-4-oxaperfluorohexylacrylate.

In US Pat. No. 2,826,584, normal 3- perfluoroalkoxy-l,l-dihydroperfluoropropyl acrylates containing 3 to 6 fully fluorinatedcarbon atoms in the molecule are described. These monomers do notcontain the terminally hydrogenated carbon atom but do possess an oxaoxygen atom in the fluorocarbon chain.

SUMMARY OF THE lNVENTlON We have discovered a new class of linearpolyperfluoropolyether monomers which can be polymerized to formelastomers.

More particularly, the monomers of the present invention comprisepolyfluorinated polyether acrylates, methacrylates, acrylamides andmethacrylamides of the formula:

wherein:

C F represents a group obtained by the opening of the double bond of ahexafluoropropylene molecule,

-C F O- and CF O are repeating oxyperfluoroalkylene units which, whensimultaneously present, are distributed randomly along the chain,

m and n may be zero or integers from l to 20 with the proviso that n andm cannot both be zero at the same time,

the sum of m+n is an integer from 1 to 20,

A is a CF or CF OCF(CF ',)--terminal group.

X is a hydrogen or fluorine atom, Y is a CF; group or may be hydrogenbut only when X is also hydrogen, and

R and R are the same or different and are hydrogen or CH Additionally,we have discovered a new class of primary and secondary polyfluorinatedpolyether alcohols which can be used to prepare the monomers of thepresent invention. These alcohols have the formula:

wherein: D is a CF -CH(OH)CF or -CF CH- 0H group, and wherein A, m and nare as above defined.

We have further discovered a new class of elastomeric polymers and amethod for preparing such polymers using the monomers of the presentinvention.

The polymers of the acrylates, methacrylates, acrylamides andmethacrylamides of the present invention possess varying molecularweights, depending on the conditions under which the polymer isobtained. The molecular weights, as determined by measurement of theintrinsic viscosity, can vary from a value from about ten thousand toseveral hundreds of thousands.

These polymers are elastomers and exhibit a range of useful properties.Such polymers are highly flexible at temperatures low as or lower than-C, and possess excellent resistance to thermal degradation even in thepresence of air at temperatures up to 250C, excellent oil-repellingproperties and resistance to attack by mineral and vegetable oils, ahigh insolubility in all of the common organic solvents, a highresistance to oxidizing agents, and excellent physical surfaceproperties resulting in surprisingly low values of the critical surfacetension of wettability of films prepared from such polymers.

The polymers of the present invention are particularly suitable forimparting soil and moisture resistance to fabrics. Usually, the fabricis impregnated with the polymer of the present invention. Methods foraccomplishing such impregnation are well known in the art, the mostcommon being simply dipping the fabric in a solution of the polymer in asuitable solvent and drying the fabric.

Fabrics treated in this manner with the polymers of the presentinvention not only exhibit high initial water, oil and soil resistance,but also retain the high levels of resistance after repeated washings.

DESCRlPTlON OF THE PREFERRED EMBODIMENTS Preferred acrylate andmethacrylate monomers of the present invention may be represented by theformula:

wherein A. X, Y. R, m and n are as defined hereinabove.

The above esters are prepared by esterifying acrylic or methacrylic acidwith an alcohol of by formula (2) 5 CH OH F 0 CF F 0 -CF cn OH c 3 2 i)3 2 2 l 2 l CF3 CF3 CF 0 (CF 0) -CF CH OH CF 0 (CF 0) CF CH OH l,l-dihydro-3 ,6-dioxa-4 -perfluoro methyl-octafluoroheptdanol-l1,1dihyd:o3,6,9- trioxa-4,7-diper fluoromethylunde:a.fluolrcv-decanql--l triper fluoromethyl-tetradecafluorotridecanol-l2-hydro4,7dioxa-S-perfluoromethylundecafluoro-octanol-Z 2-hydro-4 ,7,9-trioxa-5 ,8-

diperflmmmethyl dodeeailuoro- 2-hydro4 ,7 ,lO-trioxa-S ,8-

diperfluoromethyl-tetradecafluoro-undecanol-Z Z-hydro-4 ,7,lO,l3tetraoxa- 5,8 ,ll-triperfluoromethylheptadecafluo-ro-tetradecanol22-hydro-4 ,7 ,10 ,lZ-t'etraoxa-5,8-diperfluoromethyl-hexadecafluoro-tridecanol-Z fluoro-hexanol-lfluoro-octanol-l l,l- -dihydro-3 ,5,7,9tetraoxaundecafluoro-decanol-l(ontinued CF CF CFI CH on 3 2 4 2 2 oxatridecaf1uorododecano1-1 Theacrylic and methacrylic esters offormula (3) and which are derived fromthe primary or secondary alcohols of formula (2), can be obtained byusing any one of various conventional methods known in theesterification art. Such methods are described, for example, by R. B.Wagner and H. D. Zook, in Synthetic Organic Chemistry, J. Wiley, NY.1956, page 479.

In particular, the direct esterification of acrylic and methacrylic acidcan be carried out with the alcohols of formula (2) in the presence of acatalyst in an amount between about 0.0l and 5 parts per l00 parts byweight, the catalyst being a strong acid such as sulfuric acid orhydrochloric acid. Alternatively, the esterification can be performed byremoving the water produced by the esterification by azeotropicallydistilling it in the presence of benzene, methylene chloride orchloroform.

The esterification can also be effected by reacting the primary orsecondary alcohols with acrylyl or methacrylyl chloride. ln this casethe esterific'ation can be carried out in the presence or absence of anagent capable of neutralizing the hydrochloric acid produced, e.g.,pyridine, triethylamine, or the like.

The present esters can also be obtained by transesterification ofmethylacrylate or methylmethacrylate with the primary or secondarypolyfluorinated alcohols of formula (2). The transesterification can beconducted by operating in the presence of an excess of the fluorinatedalcohol and in the absence of solvents and catalysts, and by removingthe methanol formed by distillation.

Alternatively, the transesterification is' preferably carried out in thepresence of catalysts such as the mercuric salts, antimonous trioxide orthe titanium tetraalcoholates such as, for example, Ti(OiCaH1)4, inamounts between about 0.1 to 5 parts by weight per 100 parts offluorinated alcohol. The reaction can also be carried out in adissolving or dispersing medium such as benzene or toluene.

Also within the scope of formula (3) are those acrylates andmethacrylates which would appear, on the basis of their structuralformulas, to be the products of secondary perfluoropolyether alcohols ofthe formula:

These alcohols, however, are unstable and do not appear in the freestate. The acrylates and metacrylates of such perfluoroalcohols may,however, be obtained by using the technique described by A. G. Pittmanet al, in American Chemical Society, Polymer preprints", Sept. l966, 7(2), 1093. As described therein, perfluorinated polyether ketones of theformula wherein A, m and n are as defined hereinabove are reacted in anaprotic solvent medium with a stoichiometric amount of an alkalifluoride and then with an acrylyl or methacrylyl chloride or bromide.

The alkali fluoride, (represented by MP) is normally dispersed in anaprotic solvent such as an aliphatic or cycloaliphatic ether, e.g.,ethyl ether, butyl ether, dimethyloxyethane, dioxane, tetrahydrofuran oracetonitrile or N,N-dimethylformamide, and is then reacted with thepolyether ketone.

An intermediate secondary alkali perfluoro alcoholate is obtained havingthe structure:

wherein: M may be a K, Na or Ca ion and wherein A, m and n are asdefined above.

The reaction is carried out at temperatures between 0C and C, andpreferably between about 0C and 50C.

The acrylyl or methacrylyl chloride or bromide is then added to thisorganic suspension at a temperature between about 0C and 20C andthereafter the reaction is carried to completion at a temperaturebetween about 20C and 100C, to give the esters of the secondaryperfluoro alcohols.

The primary and secondary polyfluorinated polyether alcohols of theformula (2) can be prepared by chemical reduction of perfluorinatedpolyether compounds of the formula:

wherein: B is either a CF CO-CF or a CF- -COOR group wherein R is ahydrogen atom or an alkyl group containing from 1 to 3 carbon atoms, andthe other groups and indices are as defined above.

Various suitable methods may be used to obtain these polyfluoropolyetheralchols from the corresponding compounds of formula (7), for example asdescribed by A. M. Lovelace, D. A. Rausch and W. Postelnek in AliphaticFluorine Compounds, Reinhold PC, New York 1958 (page 137 and seq.), andby M. Hudlicky in Chemistry ofOrganic Fluorine Compounds, PergamonPress, London 1961 (page 157 and seq.)

Suitable reducing agents for this reaction are: molecular hydrogen inthe presence of catalysts consisting of metals ofGroup VIII of thePeriodic Table of Elements, preferably, those of the group comprisingNi, Co, Pd, Pt, Ru, Os, and Ir. These metals may be used in a finelydivided state either alone or supported on inert materials such ascarbon or diatomite. Additionally, the metals may be in the form oftheir oxides such as, e.g., Adams platinum catalyst.

The reduction may be carried out in the presence or absence of liquidsolvent or dispersing media such as ethers, cyclic and linearpolyethers, acetic acid, alcohols, water, and aliphatic orcycloaliphatic hydrocarbons.

The reaction conditions generally include temperatures between about Cand 250C, preferably between 20 and 200C. The hydrogen pressure can varybetween about and 200 atm. and preferably between about and 100 atm.

Alternatively, the reduction may be carried out in the presence ofcomplex alkali boron, or aluminum tetrahydrides such as, for example,LiBH NaBH LiAll-l at temperatures between about 0C and 100C and in thepresence of ethyl ether, dioxane, dimethoxyethane or, when NaBH is thecatalyst, water or methanol.

The acrylamides and the methacrylamides of the present invention havethe following structural formula:

wherein: A, R, R, m and n are as defined above.

These compounds are obtained by reacting either the esters of theformula (7) wherein B is CF COOR or the halides of the correspondingcarboxylic acids to transform the terminal functional group, i.e., COORor COl-lal, to an aminic group, and subsequently reacting the amine toobtain the respective acrylamides or methacrylamides.

Specifically, the acid or ester is converted to an amide or amonoalkalylamide and the amide or the monoalkylamide is then chemicallyreduced respectively to the amine or a monoalkylamine.

Finally these-latter two compounds are transformed into the desiredacrylamides or methacrylamides.

The foregoing described reactions are illustrated by the followingreaction sequence:

wherein R and R are as defined above, and W represents a halogen atom oran alkoxy group, such as, e.g., CHsO- OI C2H50.

The amidation reaction, reduction of the amide into a primary orsecondary amine, and the transformation of this latter compound into anacrylic derivative, can be carried out according to conventional methodsdescribed, for instance, by AB. Wagner and M.P. Zook, in SyntheticOrganic Chemistry, J. Wiley, New York (1953) and by A.M. Lovelace, D.A.Rausch, and W. Postelnek, in Aliphatic Fluorine Compounds, ReinholdP.C., New York (1958). More particularly, the amides or theN-alkylamides of these perfluorinated acids can be prepared inquantitative yields, starting from the acyl chlorides or fluoridesthereof or from the esters thereof, by reacting these compounds withgaseous ammonia or with primary amines, in the absence or presence ofsolvents such as aliphatic or alicyclic ethers, at temperatures fromabout 0C to about 30C.

The reduction of the amides into amines can be carried out, usually withvery high or quantitative yields, by means of alkali boron or aluminumtetrahydrides, such as LiAlH in an ethyl ether solution at temperaturesbetween about 0C and 30C. The primary and secondary amines obtainedreact easily and quantitatively with the acrylyl or methacrylyl chloridein ethyl ether solutions and in the presence of a basic substance, suchas triethylamine or pyridine.

The polyester perfluoroketones, perfluoroacids and perfluoroesters offormula (7) may be obtained by the methods described in Italian Pat.Nos. 789.22], 773,214, 774,001 and 773,920.

The acrylates, methacrylates, acrylamides and methacrylamides of thepresent invention are easily polymerized by free radical polymerization.Bulk polymerization as well as polymerization in solution, suspension oremulsion can be used for this purpose.

Suitable free radical initiators are selected from the group comprisingazo-bis-isobutyronitrile, benzoylperoxide, di-tert-butylperoxid, theborotrialkyls and oxygen, and the persulfates in the presence or absenceof ferrous sulfate.

Suitable solvents or dispcrsants include water, ethers, hydrocarbons,N,N-dimethylformamide, dimethylsulfoxide, etc. If desired, thepolymerization can be promoted by photochemical methods.

Generally, the polymerization temperatures vary between about -C, as inthe case of borotrialkyl and oxygen, and about +120C. The polyacrylatesand polymethacrylates of the primary and secondary polyfluro alcoholsrepresented by formula (2) and the polyacrylamides andpolymethacrylamides of the perfluoropolyether amines can also beobtained from polymeric intermediates.

Thus, the polymers may be obtained by transesterification or amidationof the methyl polyacrylate or polymethacrylate by a process analogous tothe transesterification and amidation of the monomeric esters.Particularly, the methyl polyester dissolved in toluene can be reactedwith an excess of polyfluorinated alcohol, in the presence of a Ti(OiC Hcatalyst or toluenesulfonic acid, or with an excess of apolyfluoropolyether amine.

Either the acrylyl or methacrylyl polychloride can be esterified oramidized in a solution of, for example, dioxane, with thepolyfluorinated amine or the alchol in the presence of a basic agent.

While not wanting to be held to any specific theory or mode of operationof the present invention, it is generally believed that the propertiesof the polymers of the present invention result from the presence of thepolyether structure forming the side groups of the polymeric chain. Itis thought that the exceptional flexibility of the polymeric products,even at low temperatures, is due to the rotational freedom of the etheroxygen atoms in the side group wherein each ether oxygen is positionedadjacent to 1 or 2 carbon atoms, as occurs more particularly when thepolyether side chain groups attached to the main polymer chain containone or more difluoromethylene oxide units, while the hexafluoropropylene oxide unit can be either present or not.

These desirable properties also occur in copolymeric products wherein atleast half of the acrylic or methaerylic units are bound to a residuecontaining the linear polyfluoro polyether structure. Said propertiesare markedly enhanced when, in the chains of copolymeric nature, morethan about 80% of acrylic or methaerylic units are bound to a residuecontaining a linear polyfluoropolyether structure.

The following examples illustrate the present invention:

EXAMPLE 1 A solution of g of pure CF OCF CF(CF- )OCF -COOH acid (b.p.166C 168C) diluted in 100 cc of ethyl ether was slowly added dropwise toa 1000 cc glass flask, provided with a stirrer, a watercooled refluxcondenser, and a dropping funnel, con taining 10 g of LiAlH dispersed in500 cc of anhydrous ethyl ether and maintained at C. The temperature wasraised until the ether refluxed and then the mixture was stirred for '2hours. At the end of this period, the mixture was cooled to 0C, and then50 cc of H 0 and then 50 cc of 20% H 50 were slowly added dropwise, todecompose and dissolve the solid compounds.

The organic layer was then separated, dried with anhydrous calciumsulfate (Drierite) and, after removal of the ethyl ether bydistillation, the residue was subjected to rectification at atmosphericpressure. A 70 g fraction having a boiling temperature of 129C 131C anda density of (1., 1.696 was separated. Gaschromatographic analysisindicated that the component was more than 98% pure. The elementalanalysis of this compound corresponded to the formula: C H F O The l.R.absorption spectrum analysis indicated the presence of the CH bond inthe 2900 3000 cm zone and in the 1440 cm zone, and the -OH group in the3350 cm zone, while the absorptions at 1790 cm", characteristic of theCOOH group, were absent.

The structure CF OCF CF(CF )OCF CH OH for this compound was confirmed byN.M.R. analysis.

A 30 g sample of the alcohol thus prepared, in the presence of 4.1 g oftriethylamine and 25 cc of ethyl ether, was reacted with 8.1 g of CH=CHCOCl at a temperature of 0C. The reaction mass was maintained for 4hours at 35C, after which it was poured into water. The organic layerwas separated and washed with an 0.5% solution of NaHCO; and then driedwith Na S0,, and rectified in a microdistiller. At 40C/1 mm Hg, 15 g ofaproduct were collected which possessed an elemental percentagecomposition corresponding to the formula: C H F O The analysis of theIR. absorption spectrum showed A sample absorptions at 1730 cm", and at1640 cm" that are characteristic of the carboxylic group and of vinylunsaturation, respectively, indicating that the product has thestructure:

CF30-CF2 -QFOCF2CH2OCOCH=CH2 A g sample of this product was placed intoa 25 cc glass vial fitted with a side inlet for the introduction of thereactants under a nitrogen atmosphere. 0.2X10' g moles of B(iC H,,)dissolved in 5 cc of benzotrifluoride were added. 2 cc of gaseous 0 werethen introduced into the vial under vacuum. The vial was then sealed andkept at a thermostatically set temperature of 30C for 4 hours.

At the end of this period, the vial was opened and the contents werepoured into methanol. A heavy, coagulated product was obtained which wasseparated from the solvent, washed and dried. 8 g of an amorphous,transparent polymer were obtained. This polymer softened at 30C and wasinsoluble in ethyl ether, acetone, dioxane, ethyl acetate, anddimethylformamide, while it was soluble in methylperfluorobutyrate andphenylfluoroform. lts intrinsic viscosity determined in phenylfluoroformat 90C was 0.15 (100 cc/g).

A solution of 3% of the polyacrylate in methylperfluorobutyrate wasspread over a clean, degreased glass plate and a film of polymerdeposited on the glass due to slow evaporation of the solvent. Thecontact angle formed on the surface of the film thus obtained wasdetermined for a number of pure liquids of the n-alkane series having aknown surface tension, e.g., hexadecane and heptane. From these anglesthe value of the surface tension, y, ='y 14 (dyne/cm), defined as thecritical surface tension, was calculated by means of the Fowkes method(see F. M. Fowkes in Contact angle, wettability and Adhesion Adv. Chem.series No. 43, A. C. S., Washington 1964 page 99, wherein y,- ascritical surface tension of wetting and y,,, as surface tension of solidsubstrate due to London dispersion forces are defined).

A sample of woolen fabric was impregnated with a solution of 3% of thepolyacrylate in benzotrifluoride,

by dipping and wringing out twice, the absorption inthe wet state being85%. Thereupon the fabric was dried by hanging it in a flowing air ovenat 110C. A sample of the fabric thus treated and containing 1.5%

- of the polyacrylate was evalulated for oil-repellency using a mixtureof by volume of Nujol mineral oil (Saybolt viscosity 360-390/38C) and60% by volume of n-heptane, at 20C (see J. H. Simmons in FluorineChemistry, Academic Pr., New York 1964, vol. 5, page 402). The fabricdid not absorb any of this mixture.

Another sample of the treated fabric was subjected to a water-repellencytest (AATCC method, No.22, 1961). The water-repellancy value thusdetermined was about 80.

EXAMPLE 2 A sample of 100 g of acid was reduced with LiAlH 10 g) inethyl ether (500 cc) at 0C, using the same apparatus and operatingprocedure as described in Example 1.

Using the same procedures described hereinabove, after fractionaldistillation, 60 g of product were obtained having an elemental analysiscorresponding to the formula: C,,H F, O and a boiling point range of166l67C/760 mm Hg. The l. R. spectrum showed absorption bands at2900-3000 cm; at 1440 cm and 3350 cm. The N. M. R. analysis confirmedthe washed first with 100 g of water and ice, and then with a 0.5%aqueous solution of NaHCO The washed residue was dried over Na SO anddistilled under a vacuum of 0.2 mm Hg. 40 g of a product were collectedat 6063C. The elemental and N. M. R. analyses of the product indicatedthe formula to be:

20 g of this product were polymerized by heating for 8 hours at 70C, inthe presence of 0.05 g of azo-bisisobutyronitrile. 12 g of a polymerwere obtained which was insoluble in acetone and CF ClCFCl but solublein phenylfluoroform and in methylperfluorobutyrate. In the lattersolvent the intrinsic viscosity of 0.28 dl/g was determined at 40C.

By determining the contact angle with hexadecane on a film of thepolymer spread on a glass plate according to the technique described inExample 1, the surface tension was calculated to be y 7 15 (dyne/cm).

The oil-repellency test was carried out according to the techniquedescribed in Example 1 on a woolen fabric containing 1.5% of thepolyacrylate of 1,1-dihydro-3,6,9-trioxa-4,7-diperfluoromethyl-undecafluorodecanol-l.

Thus tested, the fabric was completely repellent towards a mixtureconsisting of 30% by vol. of Nujol mineral oil and 70% by vol. ofn-heptane.

Another sample of the same fabric containing 1.5% of the polyacrylatewas subject to the water repellency test (AATCC method, No. 22, 1961). Awater repellency value of about 90 was thus determined.

CF COOH,

having a boiling point of 220C, was reacted for 15 hours at 80C, in a250 cc autoclave, in the presence of 1 g of PtO with hydrogen under apressure of 40 atm. 30 g of CF O(C F O) CF CH OH, having a boiling pointof 194C 196C were obtained. The structure of the alcohol was confirmedby l. R. and N. M. R. analyses.

10 g of the alcohol were reacted with a stoichiometric amount of acrylylchloride under the same conditions as in Example 1. 7 g of thecorresponding acrylate, having a boiling point of 95C 97C at 1 mm Hg.,were obtained. The acrylate was then polymerized at 80C for 5 hours inthe presence of 0.05 g of benzoyl peroxide. The polymers intrinsicviscosity determined in methylperfluorobutyrate at 40C was 0.25 dl/g.The

surface tension of the polymer was 7,, y 15.5 (dyne/cm), as determinedon a film of the polymer according to the Fowkes method, as described inExample 1.

EXAMPLE 4 g of the 10 g of the CF3O--(CF2CF-O)3CF2CH2OHperfluorobutyrate at 40C, possessed a surface tension 'Ym y of about 16(dyne/cm) as determined by the Fowkes method as described in Example 1.

A sample of cotton treated with a 3% solution of the polymethacrylate inbenzotrifluoride and dried in a flowing air oven at l 10C contained 1%ofthe polymer. This sample was subjected to the oil-repellency testaccording to the technique described in Example 1, and was completelyoil repellent towards a mixture of 30% Nujol and n-heptane.

EXAMPLE 5 100 g of a mixture of acids having the average formula:

wherein the sum of the indices m and n is from 1 to 4, with an averageratio m/n 3, and having an average equivalent acidimetric weight of 515,were reduced for 15 hours with H at 40 atm on PtO in an autoclave at C.The corresponding mixture of alcohols obtained had a boiling temperaturerange between 120C and 210C at 755 mm Hg.

A sample of 80 g of the mixture of alcohols was esterified by reactingit with 20 g of acrylyl chloride in the presence of 5 g of anhydrousBaCl After washing with H 0 and sodium bicarbonate and drying over Na SOthe product was distilled under a vacuum of 0.01 mm Hg, and a 65 gfraction was collected, this fraction having a boiling temperature inthe range between 30C and 70C and having the average formula:

wherein m and n are defined above.

50 g of this acrylate mixture were polymerized in the presence ofbenzoylperoxide (0.2 g) at 80C, for a period of 12 hours. Afterextraction with ethyl ether, 31 g of polymer were obtained.

This polymer had a rubbery appearance and was insoluble in dioxane andbutyrolactone and slightly soluble in benzotrifluoride andmethylperfluorobutyrate. A sample of this polymer began to thermallydecompose at 325C as determined in air with a 59 ADAMEL ther-vmobalance.

The glass transition temperature of the polymer as determined with aDifferential Scanning Calorimeter P.E. DSC 1 was between -90C and C. Thesurface tension of the polymer was 7 m, 14.5 (dyne/cm). as determined inaccordance with the method described in Example 1.

EXAMPLE 6 50 g of the ketone (b.p. 136C) and 5 g of carbon containing0.5% of Pd were introduced into a 100 cc lnox steel autoclave. Thecontents were put under vacuum and then H was introduced until thepressure was 50 atms. The mixture was reacted for ID hours at 40C. Atthe end of the reaction, the hydrogen was discharged, the reactionproduct was filtered from the catalytic residue and the prod uct wasthen rectified, collecting the fraction that boils between l64-165C at752 mm Hg (40 g).

The I. R. and N. M. R. spectra of this product corresponded to theformula:

CF (CF CF -CHOI-l.

b.p. l l l-l 13C at l mm Hg, were obtained.

25 g of this acrylate were polymerized in the presence of0.2 X g molesof B(nC H,,) and 2 cc of oxygen, at 30C, in 250 cc of benzotrifluoride.

The monomer solution was 70% polymerized after 8 hours of reaction. Atthis point the polymerization was stopped by blowing in air, and thesolution of the polymer and monomer was used for impregnating a sampleof a cotton fabric. The intrinsic viscosity of the polymer as determinedin phenylfluoroform at 90C was 0.2 dl/g.

After wringing and drying in a ventilated oven at llOC, theoil-repellency test was carried out as described in Example 1. A fabriccontaining about 1.2% of the polyacrylate was completely repellent to amixture of 50% Nujol and 50% by vol. n-heptane.

A film of the polymer was prepared by evaporation of a 5% solution ofthe polymer in methylperfluorobutyrate on glass. The contact angleformed with hexadecane was then determined and, using the Fowkes method,the value of the surface tension y y was calculated to be about l3(dyne/cm)'.

EXAMPLE 7 40 g of CF O(CF O) CF COOCH ester dissolved in 50 cc ofanhydrous ethyl ether were slowly added to a suspension of 4 g of LiAlH,in 250 cc of ethyl ether in a 1 liter flask provided with arefluxcondenser and mechanical stirrer. Then 20 cc of CH OH werecarefully added and then 50 cc of H 80 were added to dissolve thedecomposition products of the hydride. The organic solution wasseparated, the residue was washed with water and dried over Na' SO thenthe ethyl ether was distilled and the residue distilled under vacuum. 32g of an alcohol. having the formula CF O(CF Q) CF C- H OH and boiling at37-39C at 0.5 mm Hg were collected.

g of this alcohol were reacted with a mixture of 100 g ofmethylacrylate, 0.5 g of mercuric sulfate, 1 cc of H 80, and 0.5 g ofphenothiazine, in a 250 cc flask provided with an 8 mm diameterrectification column, filled with Helipack for a length of 30 cm. Themixture was reacted at a reflux ratio of 5:1, a temperature of 60-6lC,and under a pressure of 750 mm Hg. During the reaction, a mixture ofmethanol and methyl acrylate was withdrawn. Lastly, the excess ofmethylacrylate was removed by distillation. The l,l-dihydro-3,5,7,9-tetraoxa-perfluorodecanol-l-acrylate was then distilled undervacuum and the fraction boiling at 60-65C and 0.3 mm Hg was collected.

20 g of the acrylate comprising this fraction were polymerized in thepresence of 0.2 g of benzoylperoxide 25 at a temperature of 80C, for 5hours. The polymer obtained had a gummy consistency and an intrinsicviscosity of 0.31 dl/g in methylperfluorbutyrate at 40C.

The surface tension 7 7 of the polymer was 13.5 (dyne/cm), as determinedon a film of the polymer obtained from a 3% solution of the polymer inbenzotrifluoride, using the Fowkes method. A sample of cotton fabric wasimpregnated 'by dipping in a 3% solution of the polyacrylate inmethylperfluorobutyrate. After wringing and drying the sample fabric at110C in a ventilated oven, the fabric, containing 1.2% of polymer, wastested for oil-repellency according to the method described inExample 1. The fabric was completely oil-repellent towards a mixture of50% by volume of Nujol and 50% by volume of n-heptane.

EXAMPLE 8 The ketone having the formula CPS (b.p. -86C) was distilledover P 0 0.12 g mole of the freshly distilled ketone was introduced intoa 500 cc glass flask which was provided with a stirrer and a droppingfunnel, contained a mixture of 7 g of anhydrous potassium fluoride in ccof anhydrous N,N-dimethylformamide and the contents of which werethermostatically maintained at 0C.

This mixture was treated for 2 hours at 0C, and then, over a 3-hourperiod, the temperature was raised to 60C, to give a homogenous solutionof the potassium perfluoroalcoholate in the solvent.

The solution was then again cooled to 0C, after which 0.12 g mole ofacrylyl chloride was slowly added. During the addition of the acrylylchloride, potassium chloride formed and precipitated from the solution.At the end of the addition, the temperature was again raised to 50C overa period of 3 hours in order to complete the reaction. Thereupon themixture was poured into 500 g of water and ice, the organic layer waswashed with water and then, after drying over Na SO the mixture wasrectified. 40 g of a product boiling at 70C 72C under 15 mm Hg. werecollected. The elemental percent analysis, the IR. spectrum and theN.M.R. spectrum indicated the structure of the product to be:

which may also be written as:

CF OCF -CF-O-CF -CF (CF -O--CO--CH=CH 10 g of this acrylate werepolymerized by heating for 10 hours at 80C in the presence of 0.2 g ofbenzoylperoxide. After precipitation in methanol and drying under avacuum of 15 mm Hg. at 50C, 6 g ofa polymer were obtained, this polymerhaving a intrinsic viscosity as determined in methylperfluorobutyrate at40C of 0.26 dl/g. A film of this polymer was depositedon a glass platefrom a 3% solution of the polymer in benzotrifluoride. The contact anglewith hexadecane on this film was then determined. The surface tension,calculated according to the Fowkes method as described in Example 1, wasy y, 12.8 (dyne/cm).

EXAMPLE 9 100 g of an equimolar mixture of acids having the formulae CFO-CF O-CF COOH and CF O(C- F O) CF COOH, the mixture having a boilingpoint between 135C and 156C at a pressure of 755 mm Hg, dissolved in 100cc of anhydrous ethyl ether, were added to a mixture of 25 g of LiAlH,in 800 cc of anhydrous ethyl ether, contained in a 2 liter flask. Themixture was then allowed to react for 5 hours at reflux temperature.Thereupon the excess of the reducing agent was decomposed by slowlyadding to the mixture, which was cooled to C, 50 cc of methanol followedby 100 cc of 20% H 50 The contents of the flask were then poured intowater, and the organic phase was washed with water and then dried withNa SO The solvent was removed by distillation. On distillation at atemperature of from 105 to 135C, 85 g of a mixture of the alcohols CFO-CF O-CF CH,OH and CF O(CF O) CF C- H OH were obtained. 50 g of thismixture were reacted at 50C with 30 g of acrylyl chloride in thepresence of 2 g of anhydrous BaCl After hours of reaction, the reactionmass was poured into water and sodium bicarbonate, and the organicsolution was washed with water and then dried over Na SO The residue wasrectified, and 30 g of a fraction boiling between 35C and 45C at 15 mmHg were collected.

10 g of this fraction were polymerized in solution in 20 cc ofmethylperfluorobutryate in the presence of 0.2 g ofazo-bis-isobutyronitrile for hours at 60C. The polymerization yield was70% as determined by gravimetric analysis.

The polymer had an intrinsic viscosity as determined inmethylperfluorobutyrate at 40C of 0.35 dl/g and a surface tension 7 7,.of l4(dyne/cm)according to the Fowkes method described in Example 1.

EXAMPLE 10 and 10 parts of the ketone having the formula the mixturehaving a boiling range of from C to C (755 mm Hg), were slowlyintroduced into a 500 cc glass flask containing 14.5 g of KF. Thismixture was dispersed, with stirring, in 300 cc of anhydrousdimethoxyethane, thermostatically stabilized at 0C.

The mixture was reacted at temperatures between about 0C and 50C untilthe reaction mixture was completely dissolved (5 hours). The mixture wascooled to 0C and 21 g of acrylyl chloride were added with stirring overa l-hour period. The solution was then allowed to react for 3 more hoursat 50C.

The mixture was then poured into water and ice and the organic layer,after repeated washing with water and drying over Na SO was rectified.The fraction boiling between 60 and 80C under a vacuum of 15 mm Hg (60g) was collected.

50 g of this mixture of acrylates were placed under a nitrogenatmosphere in a quartz test tube immersed in a water baththermostatically stabilized at a temperature of 30C. The mixture wasthen polymerized by U.V. radiation using an original Hanau Q 81 quartzU.V. lamp, placed inside the water bath and arranged parallel andcoaxially to the test tube.

After 5 hours exposure, the radiation was stopped and the unreactedmonomer (20 g) was removed by evaporation at 80C under a 1 mm Hg.vacuum. The polymer, whose intrinsic viscosity inmethylperfluorobutyrate at 40C was of 0.15 dl/g. was dissolved in 1liter of methylperfluorobutyrate. Samples of cotton and wool fabricsimpregnated with this solution were completely repellent towards aliquid mixture consisting of 60 parts by volume of Nujol oil and 40parts of n-heptane.

EXAMPLE l1 3 cc of freshly distilled acrylyl chloride and a solution of50 mg of azo-bis-isobutyronitrile in 3 cc of anhydrous dioxane, wereintroduced into a 50 cc glass test tube under an atmosphere of drynitrogen. The mixture was thermostatically stabilized at 50C and wasthen allowed to react for 50 hours. At the end of the polymerization,the dioxane and the unreacted monomer were evaporated under vacuum. 2 gof polymer were obtained, which were dissolved in 25 cc of anhydrousdioxane and then admixed with a solution of 12 g of the alcohol havingthe formula CF O(C F O) CF C- H OH in 10 cc of anhydrous dioxane whichcontained 2.5 g of triethylamine.

The solution was reacted for 5 hours at reflux temperature. The reactionmixture was then poured into methanol and 12 g of polymer were obtained.This polymer possessed a carbon content of 26.2%, which corresponds to apolyacrylate in which about 95% of the carboxyl groups are esterifiedwith the fluoropoiyether alcohol.

This polymer was soluble in methylperfluorobutyrate. A 0.5% solution ofthe polymer in methylperfluorobutyrate at 30C possessed a viscosity of0.35 100 cc/g).

The contact angle of hexadecane on a film of this polymer was determinedand the surface tension, calculated according to the Fowkes method asdescribed in Example 1, was 7 y, 16.9 (dyne/cm).

EXAMPLE l2 2 of methylpolyacrylate, 10 cc of toluene, 0.1 g of Ti-(OiC;,H-,) and 20 g of the alcohol having the formula CF O(C F,,O) CF CHOH were introduced into a 50 cc flask equipped with an 8 300 mmrectification column filled with Fenske rings. The mixture was refluxedfor 2 hours, after which liquid was drawn off from the head of thecolumn at a rate of about 0.5 cc/hour. After 10 hours, 5 cc of tolueneand 5 g ofthe polyether alcohol were added to the flask and the reactionwas carried out for another 10 hours in the presence of 0.1 g of freshcatalyst. At the end of this period, the reaction mass was poured intomethanol. After drying, 1 1.5 g of polyacrylate which possessed a carboncontent of 26.5% were obtained, indicating that 90% of the carboxylgroups were esterified with the fluorinated alcohol. This polymer showedan intrinsic viscosity of 0.55

The contact angle with heptane on a film of this polymer, obtained froma solution of the polymer in methylperfluorobutyrate, was measured. Asurface tension of y,,, y, 18 (dyne/cm) was calculated using the Fowkesmethod. 1

EXAMPLE 13 A solution of 30 g of the ester having the formula CFO(C,F,,O),,CF COOCH in 50 cc of CF,C1CFC1 was slowly added over a 3 hourperiod to a mixture of 2 g of LiAlH and 250 cc of anhydrous ethyl etherin a 500 cc flask provided with a reflux condenser and a mechanicalstirrer.

The mixture was reacted at C for 3 hours and then for 3 hours at reflux.Thereafter the excess LiAll-l, was decomposed with water and 10% H 80The ether layer was washed with water until the washings were neutral.The organic solution was dried over Na SO the ethyl ether was removed bydistillation and the residue was vacuum distilled. 24 g of a fractionhaving a -b.p. between 130C and 135C at 0.2 mm Hg were obtained. Theelemental analysis and the IR. spectrum of the fraction corresponded tothe formula CF O(C F O) CF CH OH.

g of this alcohol was reacted with 1.5 g of CH =CHCOC1 in 30 cc of ethylether in the presence of 3 cc of (C H N.

The reaction was carried out under stirring at 0C for 2 hours.Thereafter, the entire reaction mixture was poured into 50 g of icewater and the organic solution was separated and dried over Na SO,. Thesolvent was distilled under vacuum, leaving the pure acrylic ester asthe residue.

The IR. spectrum of the residue showed absorptions attributable to thecarboxy group and vinyl saturation characteristic of the CF O(C F O) CFC- H OCOCH=CH structure.

' dl/g as determined in methylperfluorobutyrate at 40C.

5 g of the acrylic ester were polymerized in solution in 20 cc of methylperfluorobutyrate in the presence of 0.05 g of aZo-bis-isobutyronitrilefor 15 hours at 60C. At the end of the reaction, the polymer wascoagulated by pouring the reaction mixture into 100 cc of acetone. Thepolymer was then separated and dried. 3.2 g of dried polymer having anintrinsic viscosity as determined in methylperfluorobutyrate at C of0.22 dl/g were obtained.

A film of this polymer was obtained by evaporation ofa 2% solution ofthe polymer in methyl perfluorobutyrate on a glass plate.

From the contact angle data from this film, a surface tension of y y,-of about 13 (dyne/cm) was calculated, using the Fowkes method.

' EXAMPLE 14 A sample of 30 g of a mixture of acids having the averageformula CF O(CF,O),,(C F,,O),,,CF COOH, in which the sum of the indicesn+m is from 2 to 14 and the value of the average of the ratio m/n isabout 3. and which has an average equivalent acidimetric weight of 860,was added to a mixture of 100 cc of ethyl ether, 30 cc of CF Cl-CFC1 and2 g of LiAlH The reaction was carried out for 3 hours at a temperatureof 0C. The temperature was then raised to 35C.

After 4 hours at this temperature, the excess of LiAlH, was decomposedwith water and 10% H SO The organic layer was separated, washed withwater until the washings were neutral, and then dried over Na SOThesolvents were removed by distillation, leav ing behind the mixture ofthe corresponding alcohols as a residue.

10 g of the mixture of alcohols in a mixture of 20 cc 5 of ethyl ether,10 cc of CF ClCFCl and 3 cc of (C HQ N, were reacted at 0C with 1.3 g ofCH =CHCOCl dissolved in 10 cc of ethyl ester.

The reaction was carried out at 0C for 2 hours. The reaction product waspoured into 50 g of ice water, and the organic phase was separated andwashed with water until the washings were neutral. The solvents wereremoved by evaporation, leaving as a residue the mixture of fluorinatedacrylic esters.

5 g of this mixture of acrylic esters dissolved in 10 cc of a 1:1mixture of ethylacetate and CF Cl--CFCl were polymerized in the presenceof 0.1 X 10 g moles of B(iC.,H and 1 cc of oxygen at 30C for 10 hours.

The polymer thus obtained was coagulated by pouring the mixture into 100cc of acetone. After washing with acetone and drying, 2.5 g of polymerhaving an intrinsic viscosity as determined in phenylfluoroform at C of0.32 dl/g were obtained.

A polymer film was prepared by evaporating a 1% solution of the polymerin methylperfluorobutyrate on a glass plate. Using the contact angledata obtained from the film, a surface tension 7 y about 12 (dyne/cm)was calculated using the Fowkes method as described in Example 1.

EXAMPLE 15 54 g of the perfluoropolyether ketone having the formula CFO(C F O) CF COCF were slowly added to a suspension of 3.5 g of anhydrousKF in 50 cc of dimeth- 5 ylformamide at a temperature of 0C.

After 2 hours at room temperature, the solution became homogenous; itwas then cooled to 0C and a solution of5.4 g ofCH =CH-COCI in 10 cc ofdimethylformamide was added. This mixture was allowed to react for Ihour at C and for 2 hours at room temperature. The reaction mixture wasthen poured into 50 g of icy water, and the organic layer was separatedand washed twice with 10 cc of water. The organic solution was thendiluted with 50 cc of CF Cl-CFCl and was dried over Na SO After thesolvent was evaporated, 35 g of a residue were obtained. The l.R.spectrum corrsponded to the structure CF O(C F,,O) COCH=CH Afterdissolving g of the acrylate in 10 cc ofa mixture of 50% of CF ClCFC1,and ethylacetate, the acrylate was polymerized with 0.15 X 110' g molesof B(iC.,H,,) in the presence of 1.5 cc of oxygen at 30C for 6 hours.

At the end of the reaction, the polymer was coagulated by pouring 100 ccof acetone into the reaction mixture. After filtering and drying, 4.1 gof polymer were obtained, this polymer having an intrinsic viscosity asdetermined in phenylfluoroform at 90C of 0.25 dl/g. A film was preparedfrom a 1% solution of this polymer in methylperfluorobutyrate. Thesurface tension y y, 12.2 (dyne/cm) was determined from the contactangle data from the film using the Fowkes method.

EXAMPLE 16 55 g of CF 0 (CF -CFO) CF COOCH3 (b.p. 161162C) dissolved in50 cc of ethyl ether were introduced into a 100-cc glass flask providedwith a reflux condenser and a dipping pipe for feeding gases. A flow ofNH, gas was bubbled into this solution at 0C for 30 minutes. At the endof the bubbling, the solvent and the methyl alcohol were removed byevaporation. The solution was then diluted with an additional 20 cc ofethyl ether and this solution, containing the amide, was added withstirring, to a suspension of 6 g of LiAlH, in 300 cc of anhydrous ether,at 0C over a one hour period. The mixture was then refluxed for 3 hours.

After this period, the mixture was cooled to 0C and 10 cc of methanolwere added to it over a minute period. Then the mixture was poured into100 g of ice and water and, to the suspension thus obtained, g of a 40%NaOH solution were added, while stirring the suspension to assurecomplete dissolution of the inorganic salts.

The ether layer was then separated and the inorganic layer was extractedwith an additional 50 cc of ethyl ether. The ether layers were combinedand dried over K CO The solvent was then evaporated and the residuedistilled. 27 g ofa fraction boiling at 152C 153C were obtained. Theproduct was assigned the structure CH NH on the basis of the LR.absorptions due to the NH stretching (3200 3400 cm*) and OH stretching(2900 cm) and NH bending (1625 cm") absorptions. No absorptions in the1700 1800 cm zone,

characteristic of the starting ester carbonyl group and of the amide,were observed.

4.5 cc of acrylyl chloride dissolved in 40 cc of ether were added to asolution of 20 g of the amine having the formula CF -O(C F,,O) CF CH NHand 8 cc of triethylamine in 200 cc of ethyl ether, maintained at 0C.

This mixture was reacted for 3 hours at 0C and then for 3 hours at 25C,with stirring, during which time the chlorohydrate of triethylamineseparated out of the mixture. It was filtered from the aminechlorohydrate. and the ether solution was washed with water and thendried over Na SO After concentration and distillation, 18 g of afraction having a b.p. range between C C at 0.5 mm Hg. (233C/760 mm)were obtained.

This product was assigned the structure CF O(C F O) CF CH NHCOCH=CH onthe basis of the LR. absorptions due to NH bonds in the 3200 cm zone, tothe C--H bonds at 3000 cm, to the amide group in the 1670 and 1550 cmzone, and the absorptions in the 1600 1650 cm zone due to the NH and thedouble bond.

10 g of the acrylamide were polymerized under a nitrogen atmosphere at70C, in the presence of 004g of azo-bis-isobutyronitrile. After 20hours, the reaction mass was poured into a 1:1 mixture of methanol andether. After separation of the solvent and drying, 6 g of polymer wereobtained, which polymer was insoluble in hydrocarbons, ketones, ether,and N,N-dimethylformamide, and soluble in methylheptafluorobutyrate.

The polymer had the following elemental analysis: C 26.1%; H 1.08%(calculated values: C 26.12%; H 1.09). The intrinsic viscosity was 0.2cC/g) at 30C as determined on a 0.5% solution ofthe polymer in C F,COOCHA film of the polymer was deposited on a glass plate by evaporating a 1%solution of the polymer. The contact angle with hexadecane was measured,and the surface tension calculated according to the Fowkes method was y7 13 dyne/cm.

A 10 X 10 cm sample of cotton fabric was impregnated using a 3% solutionof the polymer in methylperfluorobutyrate. The dried fabric contained 1%by weight of the polymer. The fabric sample thus prepared possessed arepellency rating of 1 10 towards a mixture of 40% Nujol oil and 60%n-heptane (by volume). The same sample of fabric was impregnated andstained with a 10% by weight solution of olive oil in ether. The etherwas then removed by evaporation.

After drying for 1 hour, the fabric was washed by mechanically flappingthe fabric in 200 cc ofa 0.5% solution of DASH detergent solution at 22C(according to the methods outlined by J. C. Stewart and C. S. Whewell inTextile Research Journal, 20, 912, 1960, and by K. Durhan in SurfaceActivity and Detergency, MacMillan Co., London 1961, page 229).

After 30 minutes, by washing the fabric with water, drying andextracting with hot ether, it was determined that the oil had beencompletely removed during the washing.

This sample was again tested for oil repellency using the standard oilrepellency test described hereinabove. The oil repellency rating thusdetermined was 90. This indicates excellent retention of the anti-stainproperty of the fabric.

EXAMPLE 17 A sample of 20 g of the amine having the formula CF O(C F O)CF CH NH prepared according to the procedure of Example 16, was reactedin 50 cc of ethyl ether and in the presence of 12 cc of triethylaminewith 6 cc of methacrylyl chloride. After filtering the aminehydrochloride and the evaporation of the solvent, the reaction productwas distilled. 15 g of a fraction having a boiling point of 9092C at 0.5mm Hg were collected. The l.R. spectrum of this product corresponded tothe following structure:

CF30 (cF -pFo) cF ca Nacoc (CH3)=CH2 10 g of this product werepolymerized in the presence 0.050 g of benzoylperoxide at 70C. After 20hours, the mixture was washed with a 1:1 mixture of methanol and etherand dried to constant weight. 5.1 g of polymer were obtained, thispolymer having the following elemental analysis: C 27.7%; H 1.4%(calculated C 27.6%; H 1.42%). A film of the polymer was deposited on aglass plate by evaporation of a 1% solution of the polymer in CFCl CFCl, the intrinsic viscosity of which polymer, determined at 20C, was0.25 dl/g, and the contact angle with hexadecane was measured. Thesurface tension determined according to the Fowkes method as describedin Example 1 was y y, 18 (dyne/cm).

EXAMPLE 18 A slow flow of gaseous NH was introduced over a 30 minuteperiod into a 100 cc glass flask provided with a dipping pipe and with areflux condenser and containing 10 g of CF O(CF O) CF COOCH (b.p. 93C at55 mm Hg.) dissolved in 50 cc of ethyl ether. At the end of this period,the excess NH ethyl ether and methanol were evaporated. The solution wasthen diluted with an additional 20 cc of ether and. the diluted solutionwas added over a 1 hour period to a suspension of2 g of LiAlH, in ethylether, maintained with stirring, at C. The mixture was refluxed for anadditional 3 hours. Then 5 cc of methanol were added to the solution andthen the solution was poured into 100 g of water and ice. The organiclayer was separated and dried over K CO The ether was removed byevaporation and the residue was distilled. 6 g of a fraction having ab.p. of 95C 98C at 30 mm Hg. were collected. The l.R. spectrumcorresponded to the structural formula CF O(CF O) CF CH NH 5 g of thisamine were reacted with 1.5 cc of acrylyl chloride in 20 cc ofethylether containing 3 cc of triethylamine for 3 hours at 35C. Thereaction mixture was then filtered from the amine chlorohydrate, and theether solution was washed with water and dried over Na SO The solventwas then evaporated and the residue distilled. 3 g ofa fraction boilingat 9598C at 0.5 mm Hg were collected. The l.R. spectrum corresponded tothe structural formula: CF O(CF O)- CF CH NHCOCH=CH 2 g of this monomerwere polymerized under a nitrogen atmosphere in the presence of 0.02 gof azo-bisisobutyronitrile for 10 hours at a temperature of 60C. Afterwashing with a 1:1 mixture of methanol and ether and drying to constantweight, 1.1 g of a polymer were obtained. The elemental analysis of thisproduct was as follows: C 25.2%; H 1.3% (calculated C 25%; H 1.25%).

A film of this polymer was deposited on a glass plate from a 1% solutionof the polymer in methylperfluorobutyrate, the intrinsic viscosity ofwhich polymer as determined at 40C was 0.4 dl/g. and the contact anglewith hexadecane measured. The surface tension determined according tothe Fowkes method as described in Example 1 was 7,, 7 14 (dyne/cm). Asample of cotton fabric impregnated with 1%, by weight of polymer andsubjected to the oil-repellency test was completely repellent to amixture of 40% Nujol oil and 60% by volume n-heptane.

EXAMPLE 19 A solution of 20 cc of having a b.p. of l23-125C in ethylether was introduced into a cc glass flask provided with a dipping pipefor the inlet of gases and reflux condenser. A flow of gaseous CH -NHproduced from the reaction of 50 cc of a 30% aqueous solution of theamine with a 40% NaOH solution was slowly bubbled into the flask. Afterone hour, at the end of the reaction, the excess of amine, ethyl etherand methanol was evaporated. The remaining ether-amide solution wasadded dropwise with stirring to a suspension of 5 g of LiAlH in 200 ccof ether over a -1 hour period while maintaining the suspension at 0C.The reaction mixture was then refluxed for an additional 5 hours andthen cooled to 0C.

10 cc of methanol were added and the whole was poured into 100 g oficeand water. 10 cc ofa 40% solution of NaOH were added to this mixtureand, after dissolving the inorganic derivatives, the ether layer wasseparated, the ether evaporated and the residue distilled. 20 g of afraction boiling at ll4-l 16C was obtained. The l.R. spectrum ofthisfraction contained absorptions for the stretching of the N-H bonds at3350 cm" and the C-H bonds at 2900 cm". Based on the l.R. spectrum, theproduct was assigned the formula: CF OC F OCF CH NHCH To a mixture of 16g of this secondary amine, 6 cc of triethyl amine and 50 cc of ether,cooled to 0C, 4 cc of acrylyl chloride were added over a 1 hour period.The mixture was allowed to react for another 3 hours at 35C. Thereafter,the amine chlorohydrate was filtered from the reaction mixture, thesolvent was evaporated and the filtrate distilled. 12 g of a fractionboiling at 5558C/0.5 mm Hg (182C at 760 mm Hg) were obtained. The l.R.spectrum of this fraction indicated it had the formula 5 g of thismonomer, diluted in 5 cc of ethylacetate, were polymerized in aglassvial for 15 hours, in the presence of 0.05 g of B(iC H,,);, and 1cc of oxygen, at

a temperature of C. At the end of the polymerization,

.the polymer was precipitated by adding a lzl mixture of methanol andether. After filtering and drying to constant weight, 3 g of a polymerwere obtained. This polymer was insoluble in hydrocarbons and othernonfluorinated polar solvents such as ketones, ethers and esters, butwas soluble in methylperfluorobutyrate, in which solution the polymershowed at 40C an intrinsic viscosity of 0.55 dl/g.

A film of this polymer was deposited on a glass plate by evaporating a1% solution of the polymer, and the contact angle with dodecane wasmeasured. The surface tension calculated according to the Fowkes methodas described in Example 1 was 7' y, 17 (dyne/cm).

EXAMPLE 20 30 g of a mixture of acids having an average formula CF O(CFO),,(C F O),,,CF --COOH, wherein the sum of the indices m+n is from 2 to14 and the average value ofthe ratio mm is about 3, and having anaverage equivalent acidimetric weight of 860, were esterified withdiazomethane.

The esters were then dissolved in 100 cc of a 50% mixture of CF Cl--CFCland ethyl ether. The solution was then cooled to 0C and anhydrous NH,was bubbled through it for 30 minutes until the amidation reaction wascomplete as determined by l.R. spectrography. The excess ammonia wasevaporated and solvents and the methanol were evaporated under vaccum.

The amide mixture was dissolved in 50 cc of a 50% mixture of ethyl etherand CF Cl -CFCl and this solution was then added dropwise over a 2 hourperiod to a suspension of 2 g of LiAll-l, in 200 cc of ethyl ethermaintained at 0C. This mixture was then further reacted at 35C for 6hours. Thereupon, the LiAlH excess was decomposed with a 20% aqueoussolution of NaOH. The amine mixture was then separated, washed withwater and dried over K CO After evaporation of the solvents, 25 g ofresidue were obtained comprising a mixture of amines having the formulaCF O(C F O),,,(CF O),,CF,CH NH with the values of the indices m and ncorresponding to those of the starting mixture, as determined by N.M.R.analysis.

[0 g of this amine mixture were reacted with 1.5 g of CH =Cl-lCOCl in 50cc of a 50% mixture of ethyl ether and CF ClCFCl in the presence of astoichiometric amount of(C,H,, );,N at 0C. The mixture was reacted at 0Cfor 3 hours and then for 2 hours at room temperature.

The reaction mixture was then poured into 100 g of icy water, and theorganic layer was separated and washed with water, and was then driedover Na SO The solvents were then evaporated by distillation undervacuum. The residue obtained was a mixture of acrylamides as determinedby IR. analysis.

g of this mixture were dissolved in 10 cc of a 50% mixture of ethylacetate and CFCl -CF Cl and were then polymerized in a glass vial with0.] X 10 g mole of B(iC H,,) in the presence of 5 cc of dry air at roomtemperature for 6 hours.

The polymer was. coagulated with an excess of acetone. The coagulate waswashed with acetone and then dried by heating under vacuum at 30C. 2.1 gof product were obtained, this product-having an intrinsic viscosity asdetermined in methylperfluorobutyrate at 40C of 0.25 dl/g. A film ofthis polymer was prepared by evaporation of a 1% methylperfluorobutyratesolution of the polymer on a glass plate. The surface tension was 'y y13 dyne/cm calculated according to the Fowkes method as described inExample 1.

Variations can, of course, be made without departing from the spirit andscope of this invention.

Having thus described out invention, what we desire to secure by LettersPatent and hereby claim is:

l. A polymer having a molecular weight of at least about 10,000 asdetermined by measurement of the intrinsic viscosity of a solutionthereof, and which is selected from the group consisting of homopolymersof a monomer having the formula:

and copolymers of a mixture of at least two of said monomers wherein:

C F represents a group obtained by the opening of the double bond of ahexafluoropropene molecule, --C;,F,;O and CF O- are repeatingoxyperfluoroalkylene units which, when simultaneously present, aredistributed randomly along the chain,

m is zero or an integer from 1 to 20, n is an integer from l to 20, thesum of m+n is an integer from l to 20,

A is a CF;, or CF O-CF(CF terminal group,

Z is CH NR wherein R and R are the same or different and are hydrogen orCH 2. The polymer of claim I, wherein Z is CH NH--.

3. The polymer of claim 1, wherein Z is -CH N(CH- a)- 4. The polymer ofclaim 1,, wherein said repeating oxyperfluoroalkylene units are derivedfrom a mixture of monomers wherein the sum of m+n is in the range from Ito 4 and the average ratio m/n is 3.

5. The polymer of claim 1, wherein said repeating oxyperfluoroalkyleneunits are derived from a mixture of monomers wherein the sum of m+n isin the range from 2 to 14 and the average ratio m/n is about 3.

6. The copolymer ofclaim 1, in which at least half the repeating unitsare derived from said monomer.

7. The copolymer of claim 1, in which more than about of the repeatingunits are derived from said monomer.

8. The polymer of claim 1, wherein the intrinsic viscosity is measuredin a solution of said polymer in phemethylperfluorobutyrate v @253? I IUNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 864,318 v Dated February 4, 1975 Inventofls) Gerardo CAPORICCIO and E210STREPPAROLA- It is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

r. A a

Column 3, line 5: "alcohol of by formula" should read alcohol of-formulaColumn 6, line 9: "dimethyloxyethane" should read dimethoxyethane Column8, line 1: "polyester" should read polyetherI lines 23-24: "polyfluroshould read polyfluoro Column 10., line 26: ".evalulated" should readevaluated line 29: ".I.H. Simmons" should read J.I-I. Simons lines42-44:

"A sample of 10.0 g af A sample of 100 g of CF O-(CF -C|2FO) -CF C00Hacid CF3 acid" should read:

-- A sample of 100 g of cF -o-('cF cF-o) cF c00H acid Column 12, lines3-5 32 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent'No. 3, 864,318 4 Dated February 4, 1975 Inventm-(s) Gerardo CAPORICCIOand EZZ'LO STREPPAROLA It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

r- I a ""1 10 g of the 10 g of the CF -O (CF -CF-O) -CF -CH 0H shouldread:

- 10 g of the l CF -O-(CF2-CF-O) -CF CH2OH Column 12, line 52: "n aredefined" should read n are as defined Column 14, line 27:"methylperfluorbutyrate" should read methylperfluorobutyrate line 59:homogenous" should read homogeneous Column 17, line 14: "2 of" shouldread 2 of Column 18, line 37: '"ethyl ester" should read ethyl etherline 67: -"homogenous" should read homogeneous Column 19, line 4: "icy"should read ice line 9: "corrsponded" should read corresponded H050 vUNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION jam: No. 3,864,318 Dated February 4, 1975 Inventm-(s) Gerardo CAPORICCIO- and EzioSTREPPAROLA It is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

Column 21, lines 18-19: "presence 0.050" should read presence of 0.050"a Column 22, line 265 "and reflux" should read and a reflux Column 24,line 16: "out" should read our Signed and sealed this 6th day of May1975.

(SEAL) Attest:

C. MARSHALL DANN RUTH C. MASON 7 Commissioner of Patents AttestingOfficer and Trademarks

1. A POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST ABOUT 10,000 ASDETERMINED BY MEASUREMENT OF THE INTRISIC VISCOSITY OF A SOLUTIONTHEREOF, AND WHICH IS SELECTED FROM THE GROUP CONSISTING OF HOMOPOLYMERSOF A MONOMER HAVING THE FORMULA: A-C (C3F6O)M(CF2O)N-CF2-Z-CO-CR=CH2 ANDCOPOLYMERS OF A MIXTURE OF AT LEAST TWO OF SAID MONOMERS WHEREIN: C3F6REPRESENTS A GROUP OBTAINED BY THE OPENING OF THE DOUBLE BOND OF AHEXAFLUOROPROPENE MOLECULE, -C3F6O- AND -CF2O- ARE REPEATINGOXYPERFLUOROALKYLENE UNITS WHICH, WHEN SIMULTANEOUSLY PRESENT, AREDISTRIBUTED RANDOMLY ALONG THE CHAIN, M IS ZERO OR AN INTEGER FROM 1 TO20, N IS AN INTEGER FROM 1 TO 20, THE SUM OF M+N IS AN INTEGER FROM 1 TO20, A IS A CF3- OR CF3-O-CF(CF3)- TERMINAL GROUP; Z IS -CH2NR''- WHEREINR AND R'' ARE THE SAME OR DIFFERENT AND ARE HYDROGEN OR CH3.
 2. Thepolymer of claim 1, wherein Z is -CH2NH-.
 3. The polymer of claim 1,wherein Z is -CH2N(CH3)-.
 4. The polymer of claim 1, wherein saidrepeating oxyperfluoroalkylene units are derived from a mixture ofmonomers wherein the sum of m+n is in the range from 1 to 4 and theaverage ratio m/n is
 3. 5. The polymer of claim 1, wherein saidrepeating oxyperfluoroalkylene units are derived from a mixture ofmonomers wherein the sum of m+n is in the range from 2 to 14 and theaverage ratio m/n is about
 3. 6. The copolymer of claim 1, in which atleast half the repeating units are derived from said monomer.
 7. Thecopolymer of claim 1, in which more than about 80% of the repeatingunits are derived from said monomer.
 8. The polymer of claim 1, whereinthe intrinsic viscosity is measured in a solution of said polymer inphenylfluoroform, methylperfluorobutyrate or CFCl2-CF2Cl.
 9. A fabricimpregnated with the polymer of claim 1.